CN1049692C - Method for extracting mixed rare earth oxide by salmiac roasting black weathering slime - Google Patents

Abstract

The present invention relates to a method for extracting mixed rare earth oxide by calcining ammonium chloride and black weathering slime, which comprises the following steps: rare earth slime after ore washing, ammonium chloride and carbon powder are uniformly agitated; a starch solution is added to the mixtures to be vibrated into pellets calcined in a closed container; tap water is used for leaching the pellets at a leaching temperature of 80 to 90 DEG C, and the obtained leaching liquid is cooled to obtain PbCl2 crystal; H202 is used for oxidizing filter liquor after filtration; and ammonia water is used for adjusting the pH value. Rare earth is precipitated from the solution obtained by filtration after oxidation through oxalic acid. The rare earth of the oxalic acid is calcined at the temperature of 900 DEG C. The purity of the obtained mixed rare earth chloride is higher than 95%, and the total recovery rate is 86.5%.

Description

Method for extracting mixed rare earth oxide by roasting black weathered slime ammonium chloride

The invention relates to a method for extracting mixed rare earth oxide by roasting black weathered slime ammonium chloride, belonging to the technical field of rare earth metal smelting.

China is not only a large country with rare earth resources, with the rare earth storage accounting for 80% of the world, but also a large country with rare earth production export accounting for 70% of the world. The rare earth mineral can be in the occurrence state of only two rare earths, namely a mineral phase and an ion adsorption phase, in commercial utilization at home and abroad. They are bastnaesite, monazite, xenotime and ion-adsorbing type rare earth ore.

Recently, a new rare earth resource is discovered in Sichuan and Vietnam Dodoau in China, and is generated by weathering of raw ore, rare earth is endowed on Mn-Fe oxide in a colloidal phase form to form black weathered ore mud, the content of the rare earth is 2-10% REO, which is far more than 2% of rare earth industrial ore position in China, and the rare earth resource belongs to an aggregate rich in rare earth. Since rare earth is present in a colloidal phase in a finely dispersed state in the non-quality Mn-Fe oxide, and the particles are fine, all of which are 2 μm or more. It is therefore difficult to recover this portion of rare earths from black weathered slime using conventional physical methods of separation and enrichment such as flotation, magnetic separation and electrical separation and gravity separation.

According to calculation of one mining area of the Sichuan yak plateau, 10-15 ten thousand tons of ores are mined every year, black weathered slime accounts for 20% of the quantity of the ores, the black weathered slime is produced by 2-3 ten thousand tons every year, more than 1000 tons of rare earth is oxidized into more than 2000 ten thousand yuan when the rare earth is converted into RMB.

Since the discovery in 1986, the rare earth in the new occurrence state has attracted great domestic attention. It is generally accepted that wet processing is used to recover rare earths. According to the characteristic that rare earth iron manganese oxide can be dissolved in hydrochloric acid, rare earth is extracted by adopting a hydrochloric acid hot dipping method according to the characteristic that the geological team of the Sichuan regional Bureau 109 and the nuclear research institute of the Qinghua university are simultaneously high in reaction speed, and the recovery rate of the rare earth reaches 73.1%. However, because 1mol/l hydrochloric acid is used and leached at the temperature of 60-80 ℃, the consumption of the hydrochloric acid is large, and the leachate contains a large amount of Fe besides large acidity²⁺、Mn²⁺And other impurity ions bring great inconvenience to subsequent treatment, and the impurity ions such as iron and the like can be separated and removed after a large amount of ammonia is needed to adjust the pH value. The corrosion prevention of process control equipment is difficult, and the consumption of hydrochloric acid is too large, so that the cost accounting economic effect is poor, the operation environment is severe, and the process cannot be applied to production up to now. Therefore, we continue to explore new methods for recovering rare earth after funding by national science fund.

The invention aims to design a method for extracting mixed oxide rare earth by roasting black weathered slime with ammonium chloride, which changes the defects of large hydrochloric acid dosage, serious environmental pollution, poor economic benefit and severe operating environment caused by direct hot dipping by using hydrochloric acid, and develops a new low-temperature carbonization chlorination roasting to convert colloidal phase rare earth on Mn-Fe oxide in black weathered slime into rare earth chloride, and the rare earth chloride is leached by water. So that the rare earth in the black weathered slime can beindustrially utilized. Broadens the rare earth resources and comprehensively utilizes mineral resources.

The invention relates to a method for extracting mixed rare earth oxide by roasting black weathered slime ammonium chloride, which comprises the following steps:

(1) washing weathered rare earth ores to obtain black weathered slime, wherein the granularity of the black weathered slime is below-200 meshes (standard mesh screen);

(2) mixing the ore mud after ore washing with ammonium chloride and carbon powder according to the following proportion: slime, ammonium chloride: 10: 1-5, wherein the ratio of slime to carbon is 10: 0.2-1.5, adding a proper amount of pasty starch after uniformly mixing, and vibrating to form balls, so that the diameter of the ball particles is 0.5-2 cm;

(3) roasting the spherulites obtained in the step (2) in a closed container at the roasting temperature of 350-550 ℃ for 1-6 hours;

(4) after roasting, immersing the roasted product in water at the temperature of 60-90 ℃, wherein the solid-liquid weight ratio of water to roasted product is 5-10: 1, stirring for 0.5-1 hour, filtering while hot, adding water at the temperature of 80 ℃ to wash filter residue according to the weight ratio of 1: 0.3 of washing water to roasted product, combining washing liquid and leaching liquid, cooling the leaching liquid to the temperature below 20 ℃, and precipitating PbCl₂：

(5) In the above precipitation of PbCl₂Adding 0.5-2% hydrogen peroxide into the filtrate, stirring for half an hour, and filtering to remove impurities;

(6) adjusting the pH value of the filtrate obtained in the step (5) to 4-6 by using ammonia water, stirring for 1 hour, and filtering to remove impurity ions Mn²⁺Adding oxalic acid into the filtrate, dissolving the oxalic acid into a saturated solution according to the ratio of the rare earth to the oxalic acid in the solution being 1: 1.7-2, slowly adding the oxalic acid, stirring for half an hour, and clarifying for half an hour;

(7) and (4) filtering the solution obtained in the step (6), removing the filtrate, and roasting the filtrate at 850-950 ℃ to obtain the mixed rare earth oxide.

The chemical composition of the slime employed in the present invention is shown in table 1:

TABLE 1 chemical composition of rare earth slime

Composition of	SiO2	Al2O3	F2O3	FeO	MnO	MgO	CaO	PbO
									Content (wt.)	44.11	15.76	19.55	0.12	5.98	1.90	0.66	8.14
Composition of	SrO	Na2O	K2O	TiO2	P2O5	CO2	H2O	REO
									Content (wt.)	0.64	0.40	4.98	0.31	0.55	1.42	0.79	5.30

By using NH in the invention₄Cl is taken as a chlorinating agent, and the main chemical reaction is as follows:

first is NH₄Cl and Ln in the slime₂O₃Reaction:

further heating of NH₄Cl₃When the temperature is 326 ℃, the catalyst is decomposed into HCl and NH₃And further reacting the decomposed HCl with rare earth and valuable components thereof in the slime to generate soluble chloride:

thermodynamic analysis finds that SiO in the slime at the temperature of 400-600 DEG C₂，Al₂O₃And Fe₂O₃Cannot react with HCl, therefore, NH is used₄The Cl is used as a chlorinating agent to achieve the aim of selective chlorination, thereby being beneficial to the recovery of valuable elements in rare earth.

The following describes embodiments of the present invention:

example 1: weighing 10g of rare earth slime obtained by washing weathered ores on a balance, wherein the weight of the rare earth slime is NH₄1g of Cl2.5g of carbon powder, adding 8ml of 1% starch solution to prepare 5-10 mm pellets, drying the pellets at 95 ℃ for 2h, transferring the pellets to a crucible, roasting the pellets at 200 ℃ for 1h, and transferring the pellets to a crucibleRoasting in iron-made closed container at 450 deg.C for 2 hr to obtain calcine 10.5g, adding 100ml water, soaking at 90 deg.C for 30min, washing with 50ml water to obtain filtrate 136ml, and analyzing the dilute filtrateAnd (4) soil content. The leaching rate of the obtained rare earth is 88.7 percent.

Example 2: weighing 10g of rare earth slime and NH₄Cl2.5g carbon powder 1g, briquetting, drying at 95 ℃ for 2h, transferring into a crucible, roasting at 200 ℃ for 1h, transferring into an iron closed container, roasting at 500 ℃ for 2h, leaching with water, and washing to obtain the rare earth leaching rate of 92.3%.

Example 3: weighing 10g of rare earth slime and NH₄Cl2.5g carbon powder 1g, drying at 95 deg.C for 2h, calcining at 200 deg.C for 1h in crucible, calcining at 550 deg.C for 2h in iron-made closed container, leaching with water, and washing to obtain rare earth with leaching rate of 82.5%

Mixing the above solutions, heating to evaporate to 200ml, and cooling to obtain PbCl₂And crystallizing to obtain the Pb recovery rate of 72.6 percent. Further with H₂O₂Oxidizing the solution, and adjusting the pH value of the solution to 4-6 by using ammonia water to obtain MnO₂The precipitate analysis determined a manganese recovery of 76.8%. And precipitating the solution with oxalic acid to obtain rare earth oxalate. Roasting at 900 deg.c for 2 hr to obtain RE oxide with purity of 96.5% and total RE recovering rate of 86.5%.

Claims (1)

1. A method for extracting mixed rare earth oxide by roasting black weathered slime ammonium chloride is characterized by comprising the following steps:

(1) washing weathered rare earth ore to obtain black weathered slime with the granularity of below-200 meshes;

(2) mixing the ore mud after ore washing with ammonium chloride and carbon powder according to the following proportion: mixing the slurry and the ammonium chloride at a ratio of 10: 1-5, and the slurry and the carbon at a ratio of 10: 0.2-1.5 uniformly, adding a proper amount of pasty starch, and vibrating to form balls, so that the diameter of the ball particles is 0.5-2 cm;

(3) roasting the spherulites obtained in the step (2) in a closed container at the roasting temperature of 350-550 ℃ for 1-6 hours;

(4) after roasting, immersing the roasted product in water at the temperature of 60-90 ℃, wherein the solid-liquid weight ratio of water to roasted product is 5-10: 1, stirring for 0.5-1 hour, filtering while hot, adding water at the temperature of 80 ℃ to wash filter residue according to the weight ratio of 1: 0.3 of washing water to roasted product, combining washing liquid and leaching liquid, cooling the leaching liquid to thetemperature below 20 ℃, and precipitating PbCl₂；

(5) In the above precipitation of PbCl₂Adding 0.5-2% hydrogen peroxide into the filtrate, stirring for half an hour, and filtering to remove impurities;

(6) adjusting the pH value of the filtrate obtained in the step (5) to 4-6 by using ammonia water, stirring for 1 hour, and filtering to remove impurity ions Mn²⁺Adding oxalic acid into the filtrate, dissolving the oxalic acid into a saturated solution according to the ratio of the rare earth to the oxalic acid in the solution being 1: 1.7-2, slowly adding the oxalic acid, stirring for half an hour, and clarifying for half an hour;

(7) and (4) filtering the solution obtained in the step (6), removing the filtrate, and roasting the filtrate at 850-950 ℃ to obtain the mixed rare earth oxide.